Bacteriostatic cellulosic textile reacted with derivatives of dihydroxy hexachloro diphenyl methane



Patented July 10, 1951 BACTERIOSTATIC CELLULOSIC TEXTILE REACTED WITHDERIVATIVES OF DI- HYDROXY HEXACHLORO DIPHENYL lVIETHANE David M.Musser, Clemson, S. 0., assignor to Pacific Mills, Boston, Mass., acorporation of Mas sachusetts No Drawing. Application August 31, 1946,Serial No. 694,422

1 10 Claims.

The present invention relates to a new composition of matter,particularly useful as a textile finish, to processes for preparing thiscomposition, and to textile material, finished with the same,characterized by the desirable property of inhibiting the growth ofbacteria.

Pathogenic germs are frequently present in or on the surface of textilefabrics, either as a result of contact of the fabric with the humanbody, as in the case of sheets, pillow cases, towels and the like, orsimply as a result of exposure of the textile to an atmosphere in whichsuch bacteria are present. These germs cling tenaciously to the textilefibres and may, under favorable moisture and temperature conditions,spread and grow 1 colonies, which then present a serious danger of areadequately bacteriostatic in this relationship,

but the art heretofore has not succeeded in rendering textile materialspermanently bacteriostatic by treatment with them. Textiles coated withsuch materials commonly lose substantially all of their bacteriostaticproperty upon a single laundering and it is therefore necessary that theemployed in the present invention increases the coating treatment berepeated each time the textile article is laundered. Such coatingprocesses.

require considerable mechanical equipment and therefore, are not apracticable procedure in most hotels, hospitals and private homes inwhich bed linens and towels are used.

It is an object of the present invention to provide an improvedbacteriostatic compound, and process for making the same, suitable foruse in association with cellulosic materials such as textile fabrics,threads, yarns and fibers. A further object of the invention is toprovide cellulosic textile materials having improved bacteriostaticproperties and capable of retaining these properties more or lessindefinitely.

I have found that the desirable property of inhibiting the growth ofbacteria may be imparted to cellulosic material by treatment of thematerial, involving chemical reaction, in which there is attached to thecellulose molecule a hydrocarbon chain containing bactericidal andhydrophilic groups. The combination of such groups however, causing itto reach a degree of solubility undesirable in textile materials. Thecellulosic materials of the present invention provide a bacteriostaticenvironment which restricts the growth of bacteria thereon under allconditions of moisture and temperature.

The novel bacteriostatic and hydrophylic compounds of the presentinvention comprise derivatives of 2,2'-dihydroxy3,5,6,3.,5,6'-hexachlorodiphenylmethane having the general formula 01 GHc1 wherein R represents one of the group of radicals comprising CH-CHOHCHz-0CH2C1 H2CO-CH2C1 -0H,- -0CH2C1 and their higher homologues.

These bacteriostatic and hydrophilic compounds may be formed by reactingone of the hydroxyl groups of the chlorinated hydroxy diphenylmethanehaving the formula I OH OH 0] CH2- c1 I 1- 1 with chlorinated glycerin,paraformaldehyde and hydrochloric acid, or with epichlorohydrin or thelike, to form thereon a hydroxylated hydrocarbon chain. In the finishedcellulosic product this hydrocarbon chain is attached to the celluloseExample 1 2,2'-dihydroxy 3,5,6,3,5',6'-hexachlorodiphenylmethane isdissolved in ethyl alcohol and metallic sodium is added slowly to thissolution in molar covered by filtration, and the alcohol evaporated ordistilled off, leaving a residue having a melting point of 97 C. Thisresidue is dissolved in benzene and then paraformaldehyde is added tothe solution in molar proportions (1 to 2 mols of paraformaldehyde to 1mol of the compound). Gaseous hydrochloric acid is passed through thebenzene solution until the paraformaldehyde is completely dissolved. Thesolution is then neuh pyridine, using litmus paper as an indicator. 1

v The compound contained in the resulting solu-' tion may be applied totextile fabrics in any one of the three following ways, to form acellulose derivative which is bacteriostatic.

(A) Cotton fabric is pretreated with a 5% to solution of sodium acetate,and squeezed to about 100% pick-up. The treated fabric is thenimpregnated with a 1% to 21% solution of the compound in benzene. Thecloth is passed through squeeze rolls (about 80% to 100% pickup) andthen heated to about 130-150 C.

(B) The pyridine neutralized benzene solution of the bacteriostaticcompound is evaporated on a water bath and the resulting solid residuedispersed in warm water by stirring. The textile fabric to be treated ispretreated with sodium acetate as in (A) above, and then impregnatedwith the water dispersion. Thereafter the fabric is heated to 130-150 C.

(C) The pyridine neutralized benzene solution of the bacteriostaticcompound is evaporated and the resulting solid residue dispersed in awarm water solution of 5% to 10% sodium acetate. The textile fabric isimpregnated directly. without pretreatment, with the water dispersion,and the excess removed by squeezing to a pickup of about 100% and thefabric thereafter heated at 130150 C. as before.

Example 2 Cotton fabric is impregnated with caustic soda of mercerizingstrength and then exposed to gaseous epichlorohydrin at mm. pressure anda temperature of 50 C. for two hours, washed in water, soured in diluteacetic acid, washed again, and dried with a solvent (alcohol or thelike). The fabric is then refluxed for several hours in an alcoholsolution (or a carbon tetrachloride solution) of mono potassium salt of2,2'-dihydroxy 3,5,6,3' ,5 ,6 -hexachlorodiphenylmethane.

The fabrics resulting from the treatment oi the foregoing examplesexhibit very pronounced bacteriostatic properties and retain theseproperties, even after several commercial launderings.

The present invention is applicable generally to materials of acellulosic nature, either native or regenerated, on which there are freehydroxyl groups. Cellulosic textile materials, such as cotton'and othernatural products, may be treated in the form of fibers, threads, yarns,or in the piece, as a woven, braided, netted or knitted fabric. Thetreatment of this invention involves a chemical reaction upon thecellulose molecule with the production of a new substance. Thebacteriostatic qualities of this substance are not impaired by washing,dyeing or other treatments encountered in the finishing or use of themate-.

rial.

The foregoing disclosure of preferred embodiments of my invention ismade by way of illustration and not of limitation. It will beappreciated that changes may be made therein by those skilled in the artwithout departure from my invention, as expressed in the followingclaims.

I claim:

1. A cellulosic textile material which has been rendered bacteriostaticby reaction with a compound of the formula.

OH OR C] CH: C1

wherein R represents one of the group of radicals consisting ofCH2-CHOH-CH2-O-CH2CI. and

CEr-O-CHzCl O-GHzCl said textile material being of the class containingfree hydroxyl groups.

2. The method of rendering cellulosic textile materials containing freehydroxyl groups bacteriostatic which comprises treating the materialwith a compound of the formula on on wherein R represents one of thegroup of radicals consisting of CH2-CHOHCH2OCH2C1; and

cnr-o-cmcl -CHC o-cmcl under conditions inducing a reaction between thematerial and the compound.

3. The method of rendering cellulosic textile materials containing freehydroxyl groups bacteriostatic which comprises treating the material,sequentially, with a solution of sodium acetate .and a pyridineneutralized benzene solution of the compound of the formulaO-GHzCHOH-CHpO-CEC] C CH Cl Cl C] 0] GE Cl under conditions inducing areaction between the material and the compounds.

5. The method of rendering cellulosic textile materials containing freehydroxyl groups bacteriostatic which comprises exposing the material,

after the same has been impregnated with caustic soda of mercerizingstrength, to gaseous epichlorohydrin and thereafter treating thematerial with an alkali metal salt of 2,2'-dihydroxy 3,5,6,3',5',6'hexachlorodiphenylmethane under reflux conditions.

6. A cellulosic textile material containing free hydroxyl groups, whichhas been rendered bacteriostatic by reaction with the compound of theformula O-GHr-CHOH-CHz-O-CHzCl 7. A cellulosic textile materialcontaining free hydroxyl groups which has been rendered bacteriostaticby reaction with the compound of the 01 on 01 ii o-cmcl 8. The method ofrendering cellulosic textile materials containing i'ree hydroxyl groupsbacteriostatic which comprises pretreating the material with a solutionof sodium acetate and then impregnating it with an aqueous dispersion ofthe compound having the formula on o-cm-cnorpcnro-cmcl' C] CH 01 underconditions inducing a reaction between the material and the compound.

9. The method of rendering cellulosic textile materials containing freehydroxyl groupsba'cteriostatic which comprises treating the materialwith a dispersion of the compound having the formula 01 CH 01 g in anaqueous solution of sodium acetate, under conditions inducing a reactionbetween the material and the compound.

10. A cellulosic textile material of the class containing free hydroxylgroups which has been rendered bacteriostatic by reaction with anepichlorohydrin derivative of 2,2'-dihydroxy 3,5,6,3',5,6'hexachlorodiphenylmethane under conditions inducing a reaction betweenthe material and the derivative.

DAVID M. MUSSER.

REFERENCES CITED The following references are of record in the file ofthis patent:

OTHER REFERENCES Ser. No. 416,053, Schussler (A. P. C.) published June22, 1943.

Weston: Rot-Resistant Amer. Dyes Rep. 34, pp. P91-95 (February 26.1945).

Textile Materials."

1. A CELLULOSIC TEXTILE MATERIAL WHICH HAS BEEN RENDERED BACTERIOSTATICBY REACTION WITH A COMPOUND OF THE FORMULA